CN102559292A - Method of for desulfurization by wet oxidation of hydrogen sulfide at medium-high temperature - Google Patents
Method of for desulfurization by wet oxidation of hydrogen sulfide at medium-high temperature Download PDFInfo
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- CN102559292A CN102559292A CN2010105882382A CN201010588238A CN102559292A CN 102559292 A CN102559292 A CN 102559292A CN 2010105882382 A CN2010105882382 A CN 2010105882382A CN 201010588238 A CN201010588238 A CN 201010588238A CN 102559292 A CN102559292 A CN 102559292A
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Abstract
The invention relates to a new method for desulfurization by wet oxidation of hydrogen sulfide using iron-based ionic liquid at medium-high temperature. The iron-based ionic liquid is heatproof liquid with strong absorption and oxidation properties. Application of the iron-based ionic liquid can not only effectively absorb hydrogen sulfide gas within a concentration range of 0-100% at 70-240 DEG C, but also can oxidize hydrogen sulfide gas into elemental sulfur in a fast and efficient way. The sulfur is cooled and separated, and the iron-based ionic liquid is regenerated and reused after being subjected to oxygen oxidation. Adjustment of the pH of a reaction system is not needed during the process of high-temperature oxidation of hydrogen sulfide in the iron-based ionic liquid, and the acidity characteristic of the iron-based ionic liquid can avoid production of sulfur-containing by-products. Wet oxidation of hydrogen sulfide can be realized at a temperature ranging from 70 DEG C to 240 DEG C through adjustment of flow and concentration of hydrogen sulfide gas and adoption of combined process of absorption-oxidation-separation-regeneration, the desulfurization percent can reach over 99%, and no secondary pollution is produced.
Description
Technical field
The present invention relates to a kind of is the middle high temperature wet oxidation of sulfureted hydrogen desulfurization novel method of oxygenant with the iron-based ionic liquid; This method can directly adopt the desulfurization of wet oxidation process oxidation of sulfureted hydrogen under middle hot conditions; Need not to regulate the pH value; Not having by product to generate, is a kind of high temperature wet oxidation of sulfureted hydrogen removing process of green.
Technical background
The cleaning trans-utilization of coal is the important energy source technology that meets the human kind sustainable development target.Integrated gasification combined cycle for power generation technology (IGCC) but still contains H in the gasification gas because its potential worldwide receives publicity to friendly, economy and the high efficiency of environment
2S, COS, CS
2(wherein 90% is H
2S), obnoxious flavour such as HCl, HCN and NO, not only have very strong corrodibility, cause the corrosion of equipment, pipeline and gas turbine blades; And can make poisoning of catalyst; And the serious harm HUMAN HEALTH, therefore, gas purification just becomes an important step in the IGCC technology.As the integrated gasification combined cycle for power generation that development potentiality is arranged very much (IGCC) technology, if can the sulphur in the middle coal gas of high temperature be reduced to 20 * 10
-6Below, can make efficiency of energy utilization improve 2%.The sulphur that under middle hot conditions, removes in the gas is sensible heat and latent heat in order to utilize coal gas; Prevent the employed various poisoning of catalyst of subsequent reactions; Improve the efficient and the life of catalyst of catalyzed reaction; Therefore in coal gasification course, will improve the efficient that cleaning transforms if can under middle hot conditions, the sulphur in the coal gas be removed to lower level.
Coal gas desulfurization can adopt wet method and dry method to carry out.The traditional wet desulfurization is earlier coal gas of high temperature to be cooled to 30-50 ℃, again by the alkali lye absorbing hydrogen sulphide, under catalyst action, hydrogen sulfide is oxidized to sulphur, and the coal gas reheat after the desulfurization uses.But in wet desulphurization; Because the catalytic reaction system is water solution system, on the one hand along with reaction carry out the continuous dilute catalyst solution system of water byproduct, cause catalyst activity concentration to reduce; Final make-up catalyst activeconstituents constantly on production technique; The result certainly leads to a large amount of contaminated wastewater things and increases working cost, and desulfurization product sulphur recovery difficulty exists sulphur to block up and problems such as salt blocks up; Adopt wet desulphurization to need cooling down high-temperature coal gas on the other hand, increased heat exchanger, increased facility investment, lost the sensible heat in the coal gas simultaneously, reduced coal utilization thermo-efficiency.
Dry desulfurization adopts metal oxide sorbents direct desulfurization at high temperature; And save required cooling of solvent absorbing and reheat step, but sweetening agent regeneration difficulty, Sulfur capacity is relatively low; And can only be applied to smart desulfurization, its catalyzer is difficult to adapt to the atm number technological process.
Ionic liquid (ionic liquids) is called ionic liquid at room temperature again, is the material that is in a liquid state at ambient temperature, is made up of asymmetric organic cation and organic or inorganic negatively charged ion.With hydrophilic ionic liquid [bmim] Cl and FeCl
36H
2O in open environment, mix or with anhydrous FeCl
3At N
2But environment mixes iron-based ionic liquid [bmim] FeCl of hydrophobic synthetic down
4Iron-based ionic liquid [bmim] FeCl
4It is a kind of Lewis acid catalyst.It is the new desulfurization process that sweetening agent makes up nonaqueous phase wet oxidation hydrogen sulfide that Yujiang County etc. (CN200910092486.5) have invented with the iron-based ionic liquid.The characteristics of iron-based ionic liquid collection oxidisability, hydrophobicity and good stability have desulfurization under the acidic conditions, doctor solution and do not have the advantage that runs off and do not produce secondary salt.It should be noted that the ion liquid thermogravimetric analysis of iron-based shows that its decomposition temperature reaches 350 ℃, can be no more than original liquid state of maintenance and physicochemical characteristic under 240 ℃ of conditions.Therefore, the present invention's design is a sweetening agent with the iron-based ionic liquid, is being no more than the middle high temperature wet oxidation of sulfureted hydrogen desulfurization of oxidation of sulfureted hydrogen under 240 ℃ of conditions, generates the sulphur product, is that oxygenant regeneration iron-based ionic liquid recycles with oxygen in the air.In the common advantage of the collection wet desulphurization of high temperature wet oxidation of sulfureted hydrogen sulfur removal technology and dry desulfurization, both can be at direct desulfurization under the hot conditions, can satisfy the desulfurization of big flow, sulphur content is low or concentration change is big hydrogen sulfide again.
Summary of the invention
One of the object of the invention be the invention a kind of can be at the liquid oxidation sweetening agent of hot conditions stable existence.Utilize the iron-based ionic liquid being lower than the characteristics that have good high thermal stability under 240 ℃, breaking through traditional water wet desulphurization liquid can only make the desulfurization reaction temperature can be above 100 ℃ in the limitation of operation below 60 ℃.
Two of the object of the invention provides a kind of method that under middle hot conditions, removes hydrogen sulfide.The characteristic of utilizing the iron-based ionic liquid to recycle keeping its physicochemical characteristic below 240 ℃, high temperature desulfurizing novel method in the development.
Three of the object of the invention is the green desulfurization technology that makes up a kind of middle high temperature wet oxidation of sulfureted hydrogen of non-secondary pollution.In the process of middle high temperature oxidation hydrogen sulfide, need not regulate and control pH, the ion liquid acid characteristics of iron-based have been avoided the generation of by products such as thiosulphate and vitriol, are that the pyritous wet oxidation removes hydrogen sulfide technology in a kind of green and the adaptation.
Four of the object of the invention provides a kind of hydrogen sulfide oxidation sweetening novel process that integrates the advantage of smart desulfurization of high-temperature dry and the desulfurization of normal temperature wet method heavy body.Utilize the characteristics of ion liquid liquid temperature wide ranges and ferric strong oxidizing property, can provide a kind of under middle hot conditions atm number remove the hydrogen sulfide novel process.
The method of high temperature oxidation hydrogen sulfide desulfurization may further comprise the steps in the iron-based ionic liquid of the present invention:
(I) as shown in Figure 1; Reactor drum (1) is linked together the pyroceram pipe reactor of pyroceram sand filter funnel (3) and band oil bath wall by flange (2) and forms; The top of reactor drum has circulating condensing water (4), and the thermostable heat-conductive oil (5) of reactor drum realizes that with oil bath pan (6) it circulates.In reactor drum, add iron-based ionic liquid (7), hydrogen sulfide (8) is passed into reactor drum,, treat to begin desulphurization reaction after the homo(io)thermism by the ion liquid temperature of reaction of iron-based in the oil bath pan regulation and control reactor drum.
(II) the iron-based ionic liquid in the step (1) is carried out spinning, obtain sulphur simple substance, after the regeneration of the iron-based ionic liquid aerating oxygen (9) after the separation, the iron-based ionic liquid continues on for desulfurization.
The experimental implementation step of present method is following:
Step 1: the iron-based ionic liquid is injected in the reactor drum, and the utilization oil bath pan circulates thermostable heat-conductive oil between oil bath pan and reactor drum.
Step 2: open the hydrogen sulfide gas cylinder, be passed into the gas flow in the reactor drum, oxidizing reaction is taken place through flow director (10) control.
Step 3: with iron-based ionic liquid naturally cooling, sulphur in the iron-based ionic liquid is separated after the reaction, oxygen is passed into the back recycle of regenerating in the reactor drum with whizzer.
Step 4: along with the carrying out of reaction, certain hour is got the tail gas of reactor drum top at interval, with the concentration of hydrogen sulfide in trace sulfur analyzer (11) the measurement tail gas, calculates desulfurization degree.
Iron-based ionic liquid according to the invention has oxidation susceptibility and high heat stability performance; Imidazoles positively charged ion and iron(ic)chloride complex anion have stronger absorption and oxygenizement to hydrogen sulfide in the iron-based ionic liquid, can realize hydrogen sulfide oxidation removal rapidly and efficiently.Both all are wet desulphurizations to present method than the traditional wet doctor treatment; And advantage of the present invention and characteristics are: having overcome the conventional wet desulfurization can only be lower than 100 ℃ of limitations of reaction down; Improve the temperature of reaction of wet desulphurization, avoided sensible heat and the waste of latent heat in the coal gas; In the process of oxidation of sulfureted hydrogen, need not regulate and control the pH value of reaction system; Iron-based ionic liquid among the present invention is the acidic oxidation agent, can avoid the generation of by products such as thiosulphate and vitriol in the desulphurization reaction process.Above-mentioned advantage has guaranteed that the iron-based ionic liquid both can realize the hydrogen sulfide stripping efficient more than 99%, does not have by product to generate simultaneously, does not produce secondary pollution, is the hydrogen sulfide stripping technology of a green.
Further describe the present invention through accompanying drawing and embodiment below, but the present invention is not limited to following embodiment.
Description of drawings
Fig. 1. high temperature desulfurizing artwork in the iron-based ionic liquid of the present invention
Reference numeral
1. reactor drum 2. flanges 3. glass sand filter funnels
4. condensing works communicating vessels conduit 5. thermostable heat-conductives oil 6. oil bath pans
7. iron-based ionic liquid 8. hydrogen sulfide gas cylinders 9. oxygen cylinders
10. flow director 11. miniature sulphur analysers
Fig. 2. the ion liquid thermal multigraph of iron-based
Fig. 3. the Raman spectrogram under the imidazolitm chloride ionic liquid differing temps
Fig. 4. graph of a relation between desulfurization degree and the temperature of reaction
Fig. 5. graph of a relation between desulfurization degree and the concentration
Fig. 6. graph of a relation between desulfurization degree and the flow
Embodiment
Embodiment 1.
With 1-butyl-3-methyl chloride for imidazoles (BmimCl) and Iron(III) chloride hexahydrate (FeCl
36H
2O) be 1: 2 synthesis iron base ionic liquid in molar ratio for raw material.Fig. 2 is to the ion liquid thermogravimetric analysis result of iron-based between 30 ℃-400 ℃.The iron-based ionic liquid does not almost take place weightless in 30 ℃-250 ℃, and the weightlessness in the time of 300 ℃ is about 0.2%, has good thermostability.
Get a little sample and in crucible, be put in the retort furnace, at a certain temperature calcination processing.Can know by Fig. 3, through retort furnace 200 ℃ handle 1h after, as broad as long between the sample when imidazolitm chloride iron-based ionic liquid and 100 ℃; And behind 250 ℃ of processing 1.5h, although the sample spectra peak has no variation, its baseline generation drift; The same with 240 ℃ alternating temperature Raman spectrum; The ion liquid mobile variation of imidazolitm chloride iron-based this moment explains that variation has taken place the ion liquid physical property of imidazolitm chloride iron-based this moment, and the use temperature of its operation cycle should be controlled at below 240 ℃.
Embodiment 2.
In reactor drum, adding the 200mL iron-based ionic liquid in the instance 1, by oil bath pan regulation and control temperature of reaction, is that the hydrogen sulfide standard gas of 10000ppm is passed in the devulcanizer with the flow of 120mL/min with concentration.Fig. 4 shows that when temperature was not less than 120 ℃, the ion liquid desulfurization degree of iron-based was all more than 99% in 2h, and elevated temperature can significantly improve its desulfuration efficiency.
Embodiment 3.
In reactor drum, adding the 200mL iron-based ionic liquid in the instance 1, is 140 ℃ by oil bath pan regulation and control temperature of reaction, with the flow of 120mL/min hydrogen sulfide standard gas is passed in the devulcanizer.Fig. 5 shows that when concentration of hydrogen sulfide was 10000ppm, in the reaction times of 2h, the decreasing ratio of hydrogen sulfide can reach 100%; When increasing to 50000ppm gradually along with the concentration of hydrogen sulfide, desulfurization degree finally is reduced to 74.4%.
Embodiment 4.
In reactor drum, adding the 200mL iron-based ionic liquid in the instance 1, is 105 ℃ by oil bath pan regulation and control temperature of reaction, is that the hydrogen sulfide standard gas of 10000ppm is passed in the devulcanizer with certain flow with concentration.Fig. 6 shows that the iron-based ionic liquid is surpassing 100 ℃ of hydrogen sulfide that can remove high flow down, and its desulfuration efficiency reduces along with the increase of hydrogen sulfide flow gradually.
Claims (9)
1. the method for high temperature wet oxidation of sulfureted hydrogen in a kind is characterized in that with the iron-based ionic liquid be oxygenant, and the novel process of wet oxidation hydrogen sulfide under 70 ℃ of-240 ℃ of conditions may further comprise the steps:
(1) iron-based ionic liquid high heat stability oxygenant is synthetic: chlorination alkyl imidazole and iron trichloride thorough mixing are stirred back preparation iron-based ionic liquid.
(2) desulphurization reaction: hydrogen sulfide fed oxidizing reaction takes place in the iron-based ionic liquid at a certain temperature.
(3) separation of product sulphur: in the differing temps scope, reaction product sulphur is separated from the iron-based ionic liquid.
(4) the ion liquid regeneration of iron-based: with oxygen is oxygenant regeneration iron-based ionic liquid, recycles then.
2. method according to claim 1 is characterized in that: the ion liquid raw material iron trichloride of described synthesis iron base is meant Iron(III) chloride hexahydrate or FERRIC CHLORIDE ANHYDROUS.The chlorination alkyl imidazole is meant the imidazole derivative that chlorination is alkyl-modified; Imidazoles is including, but not limited to the N-Methylimidazole; Also can be verivates such as N-ethyl imidazol(e) and N-NSC 158165, the chlorination alkyl also can be a chloro-hexane including, but not limited to chloro-butane; The chloro octane, alkyl chloride radical derivatives such as chlorinated dodecane.
3. method according to claim 1; It is characterized in that: the ion liquid building-up process of described iron-based is for surpassing 1: 1 (containing 1: 1) with mol ratio; But be not more than 4: 1 iron(ic)chloride and the thorough mixing reaction in open physical environment of chlorination alkyl imidazole, separate making the iron-based ionic liquid through liquid-liquid or liquid-solid phase.
4. method according to claim 1 is characterized in that: the ion liquid heat decomposition temperature of described iron-based reaches 350 ℃, and the cyclical operation temperature is no more than 240 ℃.
5. method according to claim 1 is characterized in that: the concentration range of described virgin gas hydrogen sulfide content gas is between 0-100% (volume(tric)fraction), but the operant response temperature is between 70 ℃-240 ℃.
6. method according to claim 1 is characterized in that: described desulfurization product sulphur separates with centrifugation when desulfurization reaction temperature is no more than 120 ℃, also can separate by subsidence style.
7. method according to claim 1 is characterized in that: described desulfurization product sulphur reduces the doctor solution temperature earlier to room temperature when 120 ℃-240 ℃ of desulfurization reaction temperatures, settlement separate after the crystallization of product sulphur.
8. method according to claim 1 is characterized in that: described iron-based ionic liquid can be used air, also can under 70 ℃-240 ℃ condition, carry out oxidation regeneration with purity oxygen.
9. method according to claim 1 is characterized in that: described iron-based ionic liquid directly is oxidized to simple substance sulphur with hydrogen sulfide, wherein need not regulate the ion liquid pH of iron-based.
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Cited By (6)
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| CN105080316A (en) * | 2014-04-29 | 2015-11-25 | 北京化工大学 | Desulfurizer used for removing H2S and method for removing H2S |
| CN105084319A (en) * | 2014-04-29 | 2015-11-25 | 北京化工大学 | Separating agent for separating sulfur from sulfur-containing system and method for separating sulfur |
| CN105293447A (en) * | 2015-11-20 | 2016-02-03 | 北京石油化工学院 | Method for reducing degradation of iron-based ionic liquid in process of catalytic oxidation of hydrogen sulfide |
| CN108689386A (en) * | 2017-04-12 | 2018-10-23 | 北京化工大学 | A kind of vulcanization hydrogen purification and sulphur separating technology |
| CN110702468A (en) * | 2019-09-16 | 2020-01-17 | 清华大学 | Carbon-14 sampling system adopting solid oxidant |
| CN113842775A (en) * | 2021-10-14 | 2021-12-28 | 青岛科技大学 | Method for removing hydrogen sulfide by liquid-phase catalytic oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080316A (en) * | 2014-04-29 | 2015-11-25 | 北京化工大学 | Desulfurizer used for removing H2S and method for removing H2S |
| CN105084319A (en) * | 2014-04-29 | 2015-11-25 | 北京化工大学 | Separating agent for separating sulfur from sulfur-containing system and method for separating sulfur |
| CN105080316B (en) * | 2014-04-29 | 2017-09-19 | 北京化工大学 | One kind is used to remove H2S desulfurizing agent and removing H2S method |
| CN105293447A (en) * | 2015-11-20 | 2016-02-03 | 北京石油化工学院 | Method for reducing degradation of iron-based ionic liquid in process of catalytic oxidation of hydrogen sulfide |
| CN108689386A (en) * | 2017-04-12 | 2018-10-23 | 北京化工大学 | A kind of vulcanization hydrogen purification and sulphur separating technology |
| CN108689386B (en) * | 2017-04-12 | 2020-12-11 | 北京化工大学 | Hydrogen sulfide purification and sulfur separation process |
| CN110702468A (en) * | 2019-09-16 | 2020-01-17 | 清华大学 | Carbon-14 sampling system adopting solid oxidant |
| CN113842775A (en) * | 2021-10-14 | 2021-12-28 | 青岛科技大学 | Method for removing hydrogen sulfide by liquid-phase catalytic oxidation |
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Application publication date: 20120711 |